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Crown compounds for anions. Sandwich complexes of cyclic trimeric perfluoro-o-phenylenemercury with hexacyanoferrate(III) and nitroprusside anions |
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| Authors: | IA Tikhonova KI Tugashov VM Novotortsev MYu Antipin |
| Institution: | a A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow 119991, Russia b N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Avenue 31, Moscow 119991, Russia c Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Academician Lavrent’ev Avenue 9, Novosibirsk 630090, Russia |
| Abstract: | Cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 (1) is able to bind hexacyanoferrate(III) and nitroprusside anions to form complexes {(o-C6F4Hg)3]2Fe(CN)6]}3− and {(o-C6F4Hg)3]2Fe(CN)5NO]}2−, respectively, which contain one anionic species per two macrocycles. According to X-ray diffraction data, the complexes have unusual sandwich structures wherein the anionic guest is located between the planes of two molecules of 1 and is coordinated to each of these through two types of Fe-C-N-Hg bridges. One type is the simultaneous coordination of a cyanide ligand to all three Hg centres of the cycle. The other type is the coordination of a cyanide group to a single Hg atom of the macrocycle. In both types, the bonding of the anionic guest with the macrocyclic host is accomplished with the participation of π-electrons of the cyanide ligands. The synthesized compounds are the first examples of host-guest complexes of a macrocyclic multidentate Lewis acid with anionic metal complexes. |
| Keywords: | Anionic cyanide complexes Crown compounds Iron Macrocyclic multidentate Lewis acids Mercury Sandwich complexes |
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